Ji-Yao Chen

Photophysical and photochemical studies of zinc(II) phthalocyanine derivatives—effects of substituents and solvents

The effects of substituents and solvents on the photophysical and photochemical parameters of zinc(II) phthalocyanines are reported. The complexes studied are zinc phthalocyanine (ZnPc), zinc tetra(tert-butylphenoxy)phthalocyanine [ZnPc(TBPh)4], zinc octa(methylphenoxy)phthalocyanine [ZnPc(MPh)8], zinc tetranitrophthalocyanine [ZnPc(NO2)4], zinc octachlorophthalocyanine (ZnPcCl8), zinc tetrasulfophthalocyanine [ZnPc(SO3−)4], a mixture of zinc mono-, di-, tri- and tetrasulfophthalocyanine [ZnPc(SO3−)mix] and zinc naphthalocyanine (ZnNPc). It was found that the presence of peripheral substituents on the macrocycle enhances the yield of the triplet state. Among the different substituents, the sulfonated derivative, ZnPc(SO3−)mix, has the longest triplet lifetime (τT) and the highest singlet oxygen quantum yield (ϕΔ). The near infra-red absorptions of the solvents reveal that solvents that absorb around 1100 nm (triplet energy level) and around 1270 nm (singlet oxygen energy level), quench the triplet state of the ZnPc derivative as well as singlet oxygen. Although water has a high singlet oxygen quenching effect, the ϕΔ value for ZnPc(SO3−)mix in water is still reasonably high at 0.48, which may provide an explanation for the efficient photosensitization by this molecule in photodynamic studies.

High-Photoluminescence-Yield Gold Nanocubes: For Cell Imaging and Photothermal Therapy

Gold nanocubes demonstrate unique optical properties of the high photoluminescence (PL) quantum yield and a remarkably enhanced extinction band at 544 nm. The 4 x 10(-2) PL yield, which is about 200 times higher than that of gold nanorods, allows gold nanocubes to be successfully used in cell imaging of human liver cancer cells (QGY) and human embryo kidney cells (293T) with a common method of single-photon excitation. The high extinction coefficients of gold nanocubes also facilitate them carrying out the photothermal therapy of QGY and 293T cells, showing similar photokilling efficiency as compared to gold nanorods.

Generation of singlet oxygen via the composites of water-soluble thiol-capped CdTe quantum dots-sulfonated aluminum phthalocyanines.

Singlet oxygen (1O2), one of the reactive oxygen species, plays an important role in many biomedical applications. The various compounds including the phthalocyanines, quantum dots (QDs) and QD complex, which may have potential to produce 1O2, thus received more and more attentions in recent years. By means of the direct detection of near-infrared 1270 nm, we found that the water-soluble thiol-capped CdTe QDs can photoproduce 1O2 in deuterated water with a low quantum yield (QY) of 1%. When sulfonated aluminum phthalocyanines (AlSPcs) were connected to these QDs, forming water-soluble QD-Pc composites, the 1O2 QY of the composites increased to 15% under the excitation of 532 nm, while little 1O2 production can be found for AlSPc alone at the same excitation because of the poor absorption of AlSPc in this region. The results of indirect measurements of 1O2, obtained from the photodegradation of the 1O2 chemical trap anthracene-9,10-diyl-bis-methylmalonate (ADMA), confirmed 1O2 yields in both QD and QD-Pc composite solutions. The QD-Pc composites have the advantage of extending the excitation region to 400-600 nm with remarkably enhanced extinction coefficients as compared with that of AlSPc. Therefore QD-Pc composites can fully utilize visible region light excitation to effectively produce 1O2, which may facilitate the applications of QD-Pc composites in broad areas.

Photoinduced energy transfer between water-soluble CdTe quantum dots and aluminium tetrasulfonated phthalocyanine

Thiol stabilized CdTe quantum dots (QDs) synthesized in aqueous phase were used as energy donors to aluminium tetrasulfonated phthalocyanine (AlTSPc) through fluorescence resonance energy transfer (FRET). Energy transfer occurred from the QDs to AlTSPc upon photoexcitation of the QDs. An enhancement in efficiency of energy transfer with the nature of the carboxylic thiol stabilizers on the QDs was observed. The results showed that for enhanced FRET to occur, the donor–acceptor distance has to be lower than the critical distance. The quenching constant K as well as the binding constant kb values were calculated suggesting strong interaction of the QDs with the AlTSPc. Study of the photophysics of AlTSPc in the presence of the QDs revealed a high triplet state yield, hence the possibility of using QDs in combination with phthalocyanines as photosensitizers in photodynamic therapy. The triplet state lifetimes of AlTSPc in the presence of the QDs were calculated and the lifetime in the presence of CdTe capped with 3-mercaptopropionic acid (MPA) was found to be the longest. MPA capped QD in a mixture with AlTSPc resulted in long triplet lifetime and high triplet yield of the latter, and high energy transfer efficiency, hence was found to be most suitable as a potential candidate for photodynamic therapy of cancer studies.

Cellular uptake, subcellular localization and photodamaging effect of Temoporfin (mTHPC) in nasopharyngeal carcinoma cells: comparison with hematoporphyrin derivative

Temoporfin (meta-tetra (hydroxyphenyl)chlorin; mTHPC) potentiated a 100-fold higher cytotoxic effect than hematoporphyrin derivative (HPD) on two nasopharyngeal carcinoma cell lines (HK1 and CNE2) in terms of the overall photodynamic therapy (PDT) dose. The cellular uptake, evaluated by flow cytometry and spectrophotometry demonstrated that mTHPC exhibited higher uptake ability than HPD. Confocal laser scanning microscopy detection for both the sensitizer and mitochondria probe on the same cell images revealed that both drugs accumulated diffusely in the cytoplasm and that mitochrondria is a target organelle. Photo-activation ruptured the mitochrondria, with more pronounced mitochondrial damage being observed in mTHPC-PDT course. This correlated well with the cell photokilling efficiency of mTHPC.

Synthesis of high-quality near-infrared-emitting CdTeS alloyed quantum dots via the hydrothermal method

We present a facile one-pot method to fabricate water-dispersed near-infrared-emitting (650?800?nm) CdTeS alloyed quantum dots with high photoluminescence quantum yields (PL QYs). Due to the hydrolysis of thiol ligands, the sulfur was incorporated into the CdTe nanocrystals, forming CdTeS alloyed QDs. The effects of the type of thiol ligands, ligand-to-Cd molar ratio, and precursor concentration on the QDs were investigated, and thus high-quality water-dispersed CdTeS alloyed QDs (PL QYs 68%) were prepared with a high efficiency via the hydrothermal method. Water-dispersed CdTeS alloyed QDs with excellent emissions in the near-IR spectrum window have great potential in biological and medical applications especially in in?vivo imaging.

Quantum dot-aluminum phthalocyanine conjugates perform photodynamic reactions to kill cancer cells via fluorescence resonance energy transfer

Sulfonated aluminum phthalocyanines (AlPcSs), commonly used photosensitizers for photodynamic therapy of cancers (PDT), were conjugated with amine-dihydrolipoic acid-coated quantum dots (QDs) by electrostatic binding, achieving 70 AlPcSs per QD. The AlPcS-QD conjugates can utilize the intense light absorptions of conjugated QDs to indirectly excite AlPcSs producing singlet oxygen via fluorescence resonance energy transfer (FRET), demonstrating a new excitation model for PDT. The AlPcS-QD conjugates easily penetrated into human nasopharyngeal carcinoma cells and carried out the FRET in cells, with efficiency around 80%. Under the irradiation of a 532-nm laser, which is at the absorption region of QDs but not fit for the absorption of AlPcSs, the cellular AlPcS-QD conjugates can destroy most cancer cells via FRET-mediated PDT, showing the potential of this new strategy for PDT.

Refractive index measurement for biomaterial samples by total internal reflection

The refractive index of biological tissue is a fundamental parameter in applications of optical diagnosis and laser treatments. In the present work, the refractive indices and thermo-optic coefficients of some basic biomaterials, such as blood plasma, haemoglobin solution and lipid membrane, were studied by the method of total internal reflection at the wavelengths of 532 and 632.8 nm that are the most frequently used laser wavelengths in the biomedical field. The effects of the sample concentration and the temperature on refractive index were measured, and empirical relationships were summarized, accompanied by a theoretical explanation based on molecular polarization theory. The results provide some fundamental data for the refractive indices of these biomaterials under variant conditions, and also demonstrate that the total internal reflection method is a feasible and reliable way to measure the refractive indices of biological samples.

Photostability of thiol-capped CdTe quantum dots in living cells: the effect of photo-oxidation

The photostability of thiol-capped CdTe quantum dots (QDs) in Euglena gracilis (EG 277) and human embryonic kidney (HEK 293) cells was studied. The photobleaching for the cellular QDs is dependent both on the irradiation power density and the QD local concentration. The photostability of cellular QDs is better than that of chlorophyll in EG 277 cells and of green fluorescence protein (GFP) in HEK 293 cells, and is much better than that of FITC when the local concentration of QDs is not too low. The photobleaching of cellular QDs was remarkably reduced in the nitrogen treated EG 277 cells, indicating that photobleaching in living cells mainly results from photo-oxidation. The effect of photo-oxidation on QD photobleaching was further confirmed by comparing the situations in oxygen treated and nitrogen treated QD aqueous solutions. The photobleaching rate is related to the irradiation power density and the local density of QDs. The higher irradiation power density and oxygen abundance and lower QD concentration will result in a higher photobleaching rate.

Enhancement of Intracellular Delivery of CdTe Quantum Dots (QDs) to Living Cells by Tat Conjugation

Quantum dots (QDs), as novel fluorescence probes, have shown a great potential for bio-molecular labeling and cellular imaging. To stain cellular targets, the sufficient intracellular delivery of QDs is required. In this work the tat, a typical membrane-permeable carrier peptide, was conjugated with thiol-capped CdTe QDs to form CdTe Tat-QDs, and the intracellular deliveries of CdTe QDs or CdTe Tat-QDs were compared in human hepatocellular carcinoma (QGY) cells and human breast cancer (MCF7) cells in vitro by means of confocal laser scanning microscopy. Added into the cell dishes, both QDs and Tat-QDs adhered to the outer leaflet of the plasma membrane of cells within a few minutes, but the binding amount of Tat-QDs was obviously higher than that of QDs. Then both QDs and Tat-QDs can penetrate into cells, and their cellular contents increased with incubation time but both saturated after 3 hours incubation. However the cellular levels of Tat-QDs were higher than those of QDs, with the ratio of 2.1 (±0.3) times in QGY cells and 1.5 (±0.2) times in MCF7 cells, demonstrating the enhancing effect of Tat conjugation on the intracellular delivery of QDs.